WO2023174986A1 - Système de moteur à deux combustibles - Google Patents

Système de moteur à deux combustibles Download PDF

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Publication number
WO2023174986A1
WO2023174986A1 PCT/EP2023/056564 EP2023056564W WO2023174986A1 WO 2023174986 A1 WO2023174986 A1 WO 2023174986A1 EP 2023056564 W EP2023056564 W EP 2023056564W WO 2023174986 A1 WO2023174986 A1 WO 2023174986A1
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Prior art keywords
methane
fuel
paraffinic
gasoil
engine system
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PCT/EP2023/056564
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English (en)
Inventor
Roger Francis Cracknell
Karim RASHIDMANESH
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Shell Internationale Research Maatschappij B.V.
Shell Usa, Inc.
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Publication of WO2023174986A1 publication Critical patent/WO2023174986A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/103—Oxidation catalysts for HC and CO only
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B69/00—Internal-combustion engines convertible into other combustion-engine type, not provided for in F02B11/00; Internal-combustion engines of different types characterised by constructions facilitating use of same main engine-parts in different types
    • F02B69/02—Internal-combustion engines convertible into other combustion-engine type, not provided for in F02B11/00; Internal-combustion engines of different types characterised by constructions facilitating use of same main engine-parts in different types for different fuel types, other than engines indifferent to fuel consumed, e.g. convertible from light to heavy fuel
    • F02B69/04—Internal-combustion engines convertible into other combustion-engine type, not provided for in F02B11/00; Internal-combustion engines of different types characterised by constructions facilitating use of same main engine-parts in different types for different fuel types, other than engines indifferent to fuel consumed, e.g. convertible from light to heavy fuel for gaseous and non-gaseous fuels
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02D—CONTROLLING COMBUSTION ENGINES
    • F02D19/00—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
    • F02D19/06—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed
    • F02D19/0639—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed characterised by the type of fuels
    • F02D19/0642—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed characterised by the type of fuels at least one fuel being gaseous, the other fuels being gaseous or liquid at standard conditions
    • F02D19/0644—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed characterised by the type of fuels at least one fuel being gaseous, the other fuels being gaseous or liquid at standard conditions the gaseous fuel being hydrogen, ammonia or carbon monoxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02D—CONTROLLING COMBUSTION ENGINES
    • F02D19/00—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
    • F02D19/06—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed
    • F02D19/0639—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed characterised by the type of fuels
    • F02D19/0642—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed characterised by the type of fuels at least one fuel being gaseous, the other fuels being gaseous or liquid at standard conditions
    • F02D19/0647—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed characterised by the type of fuels at least one fuel being gaseous, the other fuels being gaseous or liquid at standard conditions the gaseous fuel being liquefied petroleum gas [LPG], liquefied natural gas [LNG], compressed natural gas [CNG] or dimethyl ether [DME]
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02D—CONTROLLING COMBUSTION ENGINES
    • F02D19/00—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
    • F02D19/06—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed
    • F02D19/0639—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed characterised by the type of fuels
    • F02D19/0649—Liquid fuels having different boiling temperatures, volatilities, densities, viscosities, cetane or octane numbers
    • F02D19/0652—Biofuels, e.g. plant oils
    • F02D19/0655—Biofuels, e.g. plant oils at least one fuel being an alcohol, e.g. ethanol
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02D—CONTROLLING COMBUSTION ENGINES
    • F02D19/00—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
    • F02D19/06—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed
    • F02D19/0639—Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed characterised by the type of fuels
    • F02D19/0649—Liquid fuels having different boiling temperatures, volatilities, densities, viscosities, cetane or octane numbers
    • F02D19/0657—Heavy or light fuel oils; Fuels characterised by their impurities such as sulfur content or differences in grade, e.g. for ships
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02D—CONTROLLING COMBUSTION ENGINES
    • F02D41/00—Electrical control of supply of combustible mixture or its constituents
    • F02D41/0025—Controlling engines characterised by use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02D—CONTROLLING COMBUSTION ENGINES
    • F02D41/00—Electrical control of supply of combustible mixture or its constituents
    • F02D41/0025—Controlling engines characterised by use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
    • F02D41/0027—Controlling engines characterised by use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures the fuel being gaseous
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02D—CONTROLLING COMBUSTION ENGINES
    • F02D41/00—Electrical control of supply of combustible mixture or its constituents
    • F02D41/02—Circuit arrangements for generating control signals
    • F02D41/021—Introducing corrections for particular conditions exterior to the engine
    • F02D41/0235—Introducing corrections for particular conditions exterior to the engine in relation with the state of the exhaust gas treating apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20715—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • B01D2257/7025—Methane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2370/00—Selection of materials for exhaust purification
    • F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/12—Hydrocarbons

Definitions

  • This invention relates to a method for improving the sustainability of a dual fuel engine system .
  • Natural gas consisting mainly of methane , has a signi ficant CO2 advantage over crude oil-based fuels and burns more cleanly . Even higher CO2 advantages are provided by methane from biogas production (biomethane ) and from power-to-gas (power-to-methane ) plants . This renewable methane production is attractive as it could be done with higher ef ficiency compared to other renewable fuel production pathways .
  • Methane typically in the form of liqui fied natural gas - LNG
  • Methane has been investigated as a fuel in applications such as heavy-duty trucks , inland waterway and sea going ships , locomotives , rockets , other heavy machinery, distributed island mode power generation and potentially in aircraft .
  • the internal combustion engines and fuel systems used for these applications have traditionally been designed mostly for diesel-like fuels .
  • a dual fuel engine is operated with a first liquid fuel in combination with a second gaseous fuel .
  • the first liquid fuel is generally a sel f-ignitable fuel and the combustion ignition of that fuel is used to ignite the second gaseous fuel .
  • Methane is a greenhouse gas and any methane that is not completely combusted may be emitted from the dual- fuel engine system via the exhaust .
  • the greater level of warming potential from methane compared to CO2 may even negate the benefits of the CO2 advantage obtained by using methane instead of crude oil-based fuels .
  • Methane is also generally derived from natural gas , a fossil fuel , and the ignitable liquid fuels typically used in dual fuel systems are also typically fossil fuel derived .
  • the present invention provides a process for improving the sustainability of a dual- fuel engine system operated with a first liquid fuel and a second gaseous fuel , said process comprising providing to the engine system an EN15940 compliant paraf finic gasoil as the first liquid fuel and a gaseous fuel selected from ammonia, methanol and methane based gas as the second gaseous fuel , and combusting said fuels in an internal combustion engine system, wherein exhaust gases from combusting said fuels are contacted with a methane oxidation catalyst provided in the exhaust system of said internal combustion engine system .
  • Figure 1 is a schematic diagram illustrating a dualfuel system of the type used in the present invention .
  • Figures 2 to 6 are graphs showing the results of the Examples .
  • An improved process for operating a dual- fuel engine system operated with a first liquid fuel and a second gaseous fuel has been determined .
  • the use of a paraf finic gasoil as the first liquid fuel has been demonstrated to provide improved combustion ef ficiency ( i . e . , the extent to which the fuel is completely burned) .
  • the combination of speci fic fuel types with the use of a methane oxidation catalyst in the exhaust system of the dual- fuel engine system provides an even more ef fective way of reducing methane emissions .
  • the present process requires a paraf finic gasoil as the first liquid fuel .
  • This liquid fuel is sel f-ignitable fuel , and the combustion ignition of that fuel is used to ignite the second gaseous fuel .
  • the operation of dual fuel engines is such that the ratio of the two fuels can be varied during operation .
  • the invention presented here provides also provides a means to maximise the amount of gaseous fuel that can be used during the operation of the vehicle , whilst remaining compliant with emissions regulations .
  • the use of the paraf finic fuel improves the completeness of the combustion, thereby reducing the amount to methane that is emitted from the engine without having been combusted .
  • the presence of a methane oxidation catalyst serves to oxidise any methane that has been emitted from the engine .
  • the use of a dedicated methane oxidation catalyst recognises the particular challenges in oxidising methane .
  • the paraf finic gasoil is preferably selected from Fischer-Tropsch derived paraf finic gasoils , renewable paraf finic gasoils and mixtures thereof .
  • Renewable paraf finic gasoils are gasoils derived from a biological source or biomass through processes such as , but not limited to , hydrotreating, thermal conversion and biomass-to-liquids (BTL ) .
  • a preferred renewable paraf finic gas oil is a hydrotreated vegetable oil (HVO) derived paraf finic gasoil .
  • the HVO process is based on an oil refining technology .
  • hydrogen is used to remove oxygen from the triglyceride vegetable oil molecules and to split the triglyceride into three separate chains thus creating paraf finic hydrocarbons .
  • HVO processes are described, for example in US10941349 and US8809610 .
  • Fischer-Tropsch derived is meant that a fuel or base oil is , or derives from, a synthesis product of a Fischer-Tropsch condensation process .
  • the term “non- Fischer-Tropsch derived” may be interpreted accordingly .
  • a Fischer-Tropsch derived product may also be referred to as a GTL ( gas-to-liquid) product .
  • GTL gas-to-liquid
  • the term also covers biomass to liquid and power to liquid products .
  • the carbon monoxide and hydrogen may themselves be derived from organic or inorganic, natural or synthetic sources, typically either from natural gas or from organically derived methane. More recently techniques to derive carbon monoxide and hydrogen from other sources, including more sustainable ones are being explored and used. For example, starting with carbon dioxide and water, the water can be electrolysed to give free hydrogen, typically using electricity from a sustainable source. This hydrogen can react with the carbon dioxide in the 'reverse water shift reaction' to give a source of carbon monoxide. This carbon monoxide can then be reacted with the remaining hydrogen in the typical Fischer-Tropsch synthesis process. Because of the use of electrolysis, some of these production processes are referred to as 'power-to-liquids ' .
  • Gas oil, kerosene fuel and base oil products may be obtained directly from the Fischer-Tropsch reaction, or indirectly for instance by fractionation of Fischer- Tropsch synthesis products or from hydrotreated Fischer- Tropsch synthesis products.
  • Hydrotreatment can involve hydrocracking to adjust the boiling range (see, e. g. GB2077289 and EP0147873) and/or hydroisomerisation which can improve cold flow properties by increasing the proportion of branched paraffins.
  • EP0583836 describes a two-step hydrotreatment process in which a Fischer-Tropsch synthesis product is firstly subjected to hydroconversion under conditions such that it undergoes substantially no isomerisation or hydrocracking (this hydrogenates the olefinic and oxygen-containing components ) , and then at least part of the resultant product is hydroconverted under conditions such that hydrocracking and isomerisation occur to yield a substantially paraf finic hydrocarbon fuel or oil . Desired diesel fuel fraction ( s ) may subsequently be isolated for instance by distillation .
  • Typical catalysts for the Fischer-Tropsch synthesis of paraf finic hydrocarbons comprise , as the catalytically active component , a metal from Group VI I I of the periodic table , in particular ruthenium, iron, cobalt or nickel . Suitable such catalysts are described for instance in EP0583836 .
  • Fischer-Tropsch based process is the SMDS ( Shell Middle Distillate Synthesis ) described in " The Shell Middle Distillate Synthesis Process” , van der Burgt , et al . (vide supra ) .
  • This process also sometimes referred to as the Shell “Gas-to-Liquids” or “GTL” technology
  • produces diesel range products by conversion of a natural gas (primarily methane ) derived synthesis gas into a heavy long-chain hydrocarbon (paraf fin) wax which can then be hydroconverted and fractionated to produce liquid transport and other fuels such as gasoils and kerosene .
  • a Fischer- Tropsch derived gasoil has essentially no, or undetectable levels of, sulphur and nitrogen. Compounds containing these heteroatoms tend to act as poisons for Fischer- Tropsch catalysts and are therefore removed from the synthesis gas feed. Further, the process as usually operated produces no or virtually no aromatic components.
  • Paraffinic gasoils including Fischer-Tropsch derived paraffinic gasoils and renewable paraffinic gasoils, for use in the present invention must meet European EN 15940 specification.
  • the paraffinic gasoil will preferably consist of at least 95% w/w, more preferably at least 98% w/w, even more preferably at least 99.5% w/w, and most preferably up to 100% w/w of paraffinic components, preferably iso- and normal paraffins, preferably comprising from 80% w/w or greater of iso-paraffins.
  • the aromatics content of the paraffinic gasoil will typically be below 1% w/w, preferably below 0.5% w/w and more preferably below 0.1% w/ w .
  • paraffinic gasoils have relatively low levels of polar components, in particular polar surfactants, for instance compared to petroleum derived fuels. It is believed that this can contribute to improved antifoaming and dehazing performance.
  • polar components may include for example oxygenates, and sulphur and nitrogen containing compounds.
  • a low level of sulphur in a Fischer-Tropsch derived fuel is generally indicative of low levels of both oxygenates and nitrogen-containing compounds since all are removed by the same treatment processes .
  • a preferred paraffinic gasoil for use herein has a distillation range similar to that of a petroleum derived diesel, that is typically within the 160°C to 400°C range, preferably with a T95 of 360°C or less.
  • a preferred paraffinic gasoil for use herein will typically have a density (as measured by EN ISO 12185) of from 0.76 to 0.80, preferably from 0.77 to 0.79, more preferably from 0.775 to 0.785 g/cm 3 at 15°C.
  • a preferred paraffinic gasoil for use herein has a cetane number (ASTM D613) of greater than 70, suitably from 70 to 85, most suitably from 70 to 77.
  • a preferred paraffinic gasoil for use herein has a kinematic viscosity at 40°C (as measured according to ASTM D445) in the range from 2.0 mm 2 /s to 5.0 mm 2 /s, preferably from 2.5 mm 2 /s to 4.0 mm 2 /s.
  • a preferred paraffinic gasoil for use herein has a sulphur content (ASTM D2622) of 5 ppmw (parts per million by weight) or less, preferably of 2 ppmw or less.
  • paraffinic gasoils used herein will preferably comprise no more than 3% w/w, more preferably no more than 2% w/w, even more preferably no more than 1% w/w of cycloparaffins (naphthenes) , by weight of the paraffinic gasoils present.
  • the paraffinic gasoils used herein preferably comprise no more than 1% w/w, more preferably no more than 0.5% w/w, of olefins, by weight of the paraffinic gasoils present .
  • the paraffinic gas oil comprises, or more preferably consists essentially of, one or more hydrotreated vegetable oil (HVO) derived paraffinic gasoils .
  • HVO hydrotreated vegetable oil
  • the second gaseous fuel is selected from ammonia, methanol, hydrogen and a methane-based gas. It is preferred that the second gaseous fuel is a methane-based gas.
  • the term 'methane-based gas' means a substance which is gaseous at ambient temperature and pressure, and which comprises a large proportion of methane.
  • the term 'ambient temperature and pressure' means a temperature of 25°C (298.15K) and a pressure of 1.01325 bar.
  • the term 'a large proportion of methane' means a content of methane preferably greater than 70 vol%, more preferably greater than 80 vol%, and most preferably greater than 90 vol%, based on the total amount of methane-based gas.
  • the methane-based gas for use herein is preferably selected from natural gas, renewable methane gas, such as biomass-derived methane, synthetic methane from methanation processes, and mixtures thereof.
  • the methane-based gas is derived from a renewable process.
  • Methane-based gas may alternatively comprise mixtures of natural gas and hydrogen in any quantity in which natural gas is present at a level at which a methane oxidation catalyst is necessary to prevent methane emissions.
  • the overall combined proportion of methane and hydrogen in the mixture means a content of methane/hydrogen combined preferably greater than 70 vol%, more preferably greater than 80 vol%, and most preferably greater than 90 vol%, based on the total amount of methane-based gas.
  • the methane-based gas may be provided as a compressed gas, e.g., compressed natural gas (CNG) , or a liquified gas, e.g., liquified natural gas (LNG) .
  • a compressed gas e.g., compressed natural gas (CNG)
  • a liquified gas e.g., liquified natural gas (LNG)
  • both the first liquid fuel and the second gaseous fuel are produced from renewable resources .
  • the first liquid fuel comprises an HVO-derived paraf finic gasoil and the second gaseous fuel comprises a biomass-derived methane .
  • additives may be added to either or both of the first liquid fuel or the second gaseous fuel or the combination thereof in order to improve the process of operating the dual- fuel engine system .
  • Such additives would be well known to the person skilled in the art and include , but are not limited to , detergents , corrosion inhibitors , viscosity index improvers , anti- foam agents , dispersants , friction modi bombs , odorisers , colourants and the like .
  • the combination of fuels is combusted in an internal combustion engine system .
  • a combustion engine may be of a standard type that is used in road transport , marine , mining, rail and aircraft applications . Modi fications may be made to the engine system to facilitate the use of dual- fuel .
  • a methane oxidation catalyst in the exhaust system of the internal combustion engine system .
  • a catalyst may be any suitable catalyst capable of converting low levels of methane in exhaust gases to carbon dioxide and hydrogen .
  • Such catalysts may be produced from noble metals and zirconia, for example according to US20190022625 or W02018041630 .
  • the exhaust gas handled by the exhaust system of the dual- fuel engine system contains a methane concentration of less than or equal to 10000 ppm by volume (ppmv) , preferably in the range of from 25 ppmv to 10000 ppmv, more preferably of from 50 to 5000 ppmv and even more preferably from 100 to 3000 ppmv.
  • ppmv ppm by volume
  • the methane in the exhaust gas is contacted with oxygen in the presence of the methane oxidation catalyst in order to convert said methane into carbon dioxide and water.
  • the methane and oxygen are contacted with the methane oxidation catalyst in a O2 : CH4 ratio at least 2:1, more preferably at least 10: 1, even more preferably at least 30: 1, still even more preferably at least 50:1, yet more preferably at least 100:1.
  • the methane and oxygen are contacted with the methane oxidation catalyst in a O2 : CH4 ratio of in the range of from 2:1 to 200:1, more preferably of from 10:1 to 200:1, even more preferably of from 30:1 to 200:1, still even more preferably of from 50:1 to 200:1, yet more preferably if from 100:1 to 200:1.
  • the methane and oxygen are contacted with the methane oxidation catalyst at a temperature in the range of from 120 to 650°C, more preferably of from 250 to 650°C, still more preferably 300 to 600°C.
  • the oxygen used to oxidize the methane may be provided as part of the exhaust gas, and/or from an external source, such as air, oxygen enriched air, pure oxygen or mixtures of oxygen with one or more other, preferably inert, gases.
  • an external source such as air, oxygen enriched air, pure oxygen or mixtures of oxygen with one or more other, preferably inert, gases.
  • part or all of the oxygen is provided from a source other than an exhaust gas it may be advantageous to preheat the oxygen prior to contacting the oxygen with the methane.
  • Figure 1 provides a schematic illustration of a dual-fuel engine system operated by a process according to the present invention.
  • the illustration is exemplary and not intended to limit the invention in any way.
  • Compressed natural gas (1) is provided via a pressure regulator (2) to a natural gas injector (3) .
  • the natural gas (4) is then injected into an air stream, which has been cleaned via an air filter (5) , to form a natural gas/air mixture (6) .
  • the natural gas/air mixture (6) is then provided to the combustion chamber (7) of an engine (8) , wherein it is mixed with a diesel stream (9) from a diesel injector (10) .
  • the engine (8) may also be fitted with an angle encoder (11) , a combustion analyser (12) and a dynamometer (13) to track the combustion of the air/diesel/natural gas mixture and the action of the engine (8) .
  • Exhaust gases (14) from the combustion chamber (7) are then passed into an exhaust system (15) .
  • the exhaust system (15) contains a methane oxidation catalyst
  • the exhaust (18) of the system will contain very low levels of methane.
  • the Examples were performed using various fuel combinations of methane with diesel fuels. Both mineral diesel fuels and EN15940-compliant paraffinic diesel gasoils were tested.
  • the test engine used was a model year 2010 Euro 5 four-cylinder 2.2 Litre Ford Puma diesel equipped with common rail direct fuel injection, a variable geometry turbocharger and cooled external Exhaust Gas Recirculation (EGR) . Key specifications of the engine are provided in Table 1 below. The engine was equipped with gaseous port fuel injection and associated control. Table 1 - Engine specifications
  • test rig incorporated a DC dynamometer for controlling the speed and load and was accompanied by a standard industry set up for coolant fluid control and key measurements of torque, fuel consumption, engine performance and emissions.
  • Dual-fuel experimental work implemented Premixed Dual-Fuel Combustion (PDFC) with two pilot injections, with the first injection premixed prior to the second injection with a 50/50 ratio in quantity.
  • PDFC tests were undertaken at 1200 rpm/ 5.3 bar BMEP. Methane in 99.95 %vol. was stored in gas bottles at 200 bar maximum pressure and supplied through the gaseous fuel delivery system, injected to the inlet of the intake manifold. The diesel rail pressure was kept fixed at 600 bar while the average pressure of the intake manifold was again held to 1.3 bar.
  • the PDFC tests were undertaken under a 58% ( ⁇ 2) natural gas substitution ratio (by energy) .
  • samples were taken at the exhaust port after the turbine by two sampling probes , one for the gas analyser and another one for the smoke meter .
  • FIGS. 2 to 5 show the exhaust gas emissions during
  • EN15940 paraffinic diesel-PDFC and diesel PDFC and figure 6 shows the combustion efficiency during EN15940 paraffinic diesel-PDFC and diesel PDFC tests.
  • the x-axis of each of those Figures is labelled Pilot Separation and is measured in °CA.
  • EN15940 paraffinic diesel gasoil and diesel are referred to as pilot fuels. Pilot separation refers to the difference in °CA between combustion of the pilot fuel and the combustion of the premixed gaseous fuel.
  • the y-axes of Figures 2, 3 and 4 are labelled brake specific carbon monoxide (BSCO) , brake specific hydrocarbon (BSHC) and brake specific oxides of nitrogen (BSNO X ) respectively and are all measured in g/kWh.
  • BSCO brake specific carbon monoxide
  • BSHC brake specific hydrocarbon
  • BSNO X brake specific oxides of nitrogen
  • Figures 2 to 5 show that using EN15940 paraf finic diesel as the pilot fuel generally results in lower emissions compared to using diesel .
  • the lower CO and THC emissions for EN15940 paraf finic diesel-PDFC indicate a higher combustion ef ficiency compared to diesel-PDFC since there is less unburned CO and hydrocarbons .
  • Those figures indicate that 40 °CA pilot separation is the optimum operating condition since it results to the lowest CO, THC, NOx and FSN values with both EN15940 paraf finic diesel and diesel as pilot fuels .
  • Better fuel atomisation and entrainment of the inj ected pilot fuel within the premixed gaseous fuel provided more ignition sources for the surrounding gaseous fuel , thus improving flame propagation and the subsequent improvement in emissions and combustion ef ficiency .
  • Figure 6 shows that using EN15940 paraf finic diesel gasoil as the pilot fuel results to higher combustion ef ficiency compared to using diesel .
  • a process for improving the sustainability of a dualfuel engine system operated with a first liquid fuel and a second gaseous fuel comprising providing to the engine system an EN15940 compliant paraf finic gasoil as the first liquid fuel and a gaseous fuel selected from ammonia, methanol and methane based gas as the second gaseous fuel , and combusting said fuels in an internal combustion engine system, wherein exhaust gases from combusting said fuels are contacted with a methane oxidation catalyst provided in the exhaust system of said internal combustion engine system.
  • said EN15940 compliant paraffinic gasoil comprises either a fossil derived Fischer-Tropsch derived paraffinic gasoil, a renewable paraffinic gasoil, or mixtures thereof.

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Abstract

L'invention concerne un procédé permettant d'améliorer la durabilité d'un système de moteur à deux combustibles fonctionnant avec un premier combustible liquide et un second combustible gazeux, ledit procédé consistant à fournir au système de moteur un gasoil paraffinique conforme à la norme EN15940 en tant que premier combustible liquide et un combustible gazeux choisi parmi un gaz à base d'ammoniac, de méthanol, d'hydrogène et de méthane en tant que second combustible gazeux, et à brûler lesdits combustibles dans un système de moteur à combustion interne, les gaz d'échappement provenant de la combustion desdits combustibles étant mis en contact avec un catalyseur d'oxydation de méthane disposé dans le système d'échappement dudit système de moteur à combustion interne.
PCT/EP2023/056564 2022-03-17 2023-03-15 Système de moteur à deux combustibles WO2023174986A1 (fr)

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